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A conformational study of N-acetyl glucosamine derivatives utilizing residual dipolar couplings
(2011)
The conformational analyses of six non-rigid N-acetyl glucosamine (NAG) derivatives employing residual dipolar couplings (RDCs) and NOEs together with molecular dynamics (MD) simulations are presented. Due to internal dynamics we had to consider different conformer ratios existing in solution. The good quality of the correlation between theoretically and experimentally obtained RDCs show the correctness of the calculated conformers even if the ratios derived from the MD simulations do not exactly meet the experimental data. If possible, the results were compared to former published data and commented.
How much is too much? - a case report of nutritional supplement use of a high-performance athlete
(2011)
Although dietary nutrient intake is often adequate, nutritional supplement use is common among elite athletes. However, high-dose supplements or the use of multiple supplements may exceed the recommended daily allowance (RDA) of particular nutrients or even result in a daily intake above tolerable upper limits (UL). The present case report presents nutritional intake data and supplement use of a highly trained male swimmer competing at international level. Habitual energy and micronutrient intake were analysed by 3 d dietary reports. Supplement use and dosage were assessed, and total amount of nutrient supply was calculated. Micronutrient intake was evaluated based on RDA and UL as presented by the European Scientific Committee on Food, and maximum permitted levels in supplements (MPL) are given. The athlete's diet provided adequate micronutrient content well above RDA except for vitamin D. Simultaneous use of ten different supplements was reported, resulting in excess intake above tolerable UL for folate, vitamin E and Zn. Additionally, daily supplement dosage was considerably above MPL for nine micronutrients consumed as artificial products. Risks and possible side effects of exceeding UL by the athlete are discussed. Athletes with high energy intake may be at risk of exceeding UL of particular nutrients if multiple supplements are added. Therefore, dietary counselling of athletes should include assessment of habitual diet and nutritional supplement intake. Educating athletes to balance their diets instead of taking supplements might be prudent to prevent health risks that may occur with long-term excess nutrient intake.
Amphiphilic linear ternary block copolymers (ABC) were synthesized in three consecutive steps by the reversible addition fragmentation chain transfer (RAFT) method. Using oligo(ethylene oxide) monomethyl ether acrylate, benzyl acrylate, and 1H,1H-perfluorobutyl acrylate monomers, the triblock copolymers consist of a hydrophilic (A), a lipophilic (B), and a fluorophilic (C) block. The block sequence of the triphilic copolymers was varied systematically to provide all possible variations: ABC, ACB, and BAC. All blocks have glass transition temperatures below 0 degrees C. Self-assembly into spherical micellar aggregates was observed in aqueous solution, where hydrophobic cores undergo local phase separation into various ultrastructures as shown by cryogenic transmission electron microscopy (cryo-TEM). Selective solubilization of substantial quantities of hydrocarbon and fluorocarbon low molar mass compounds by the lipophilic and fluorophilic block, respectively, is demonstrated.
1-Oxo-1,3-dithiolane (4) and its cis- and trans-2-methyl (5,6), -4-methyl (7,8) and -5-methyl (9,10) derivatives were prepared by oxidizing the corresponding 1,3-dithiolanes (1-3) with NaIO(4) in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with (1)H and (13)C NMR spectroscopy and molecular modelling. The sulfoxides 4-6 and 8-10 attain two S(1) type envelopes (sometimes slightly distorted) the S=O(ax) envelope greatly dominating. Cis-4-methyl-1-oxo-1,3-dithiolane is a special case exhibiting both two closely related S=O(ax) (30 and 27%) as well as S=O(eq) (21 and 22%) forms [S(1) and C(4) envelopes, respectively]. The relative energies of these conformations, the values of (1)H-(1)H coupling constants and (1)H and (13)C chemical shifts were estimated by computational methods and they support well the conclusions based on the experimental data.
Background: The elderly need strength training more and more as they grow older to stay mobile for their everyday activities. The goal of training is to reduce the loss of muscle mass and the resulting loss of motor function. The dose-response relationship of training intensity to training effect has not yet been fully elucidated.
Methods: PubMed was selectively searched for articles that appeared in the past 5 years about the effects and dose-response relationship of strength training in the elderly.
Results: Strength training in the elderly (> 60 years) increases muscle strength by increasing muscle mass, and by improving the recruitment of motor units, and increasing their firing rate. Muscle mass can be increased through training at an intensity corresponding to 60% to 85% of the individual maximum voluntary strength. Improving the rate of force development requires training at a higher intensity (above 85%), in the elderly just as in younger persons. It is now recommended that healthy old people should train 3 or 4 times weekly for the best results; persons with poor performance at the outset can achieve improvement even with less frequent training. Side effects are rare.
Conclusion: Progressive strength training in the elderly is efficient, even with higher intensities, to reduce sarcopenia, and to retain motor function.
Rotation about the single bond adjoining the aryl and fluorene moieties in 9-arylfluorenes can be frozen out on the NMR timescale if methyl groups are located at either one or both of the ortho positions of the aryl substituent. In the ground-state of these rotamers, the planes of the aryl and fluorene moieties are perpendicular to each other and the methyl substituents are consequently positioned either above the fluorene moiety or in-plane with it; thus, the methyl protons are either shielded or deshielded, respectively, due to the ring current effect of the fluorene moiety. This anisotropic effect on the H-1 chemical shifts of the methyl protons has been quantified on the basis of through-space NMR shieldings (TSNMRS) and subsequently Delta delta(calcd) compared with the experimentally observed chemical shift differences, Delta delta(exp). In this context, the experimental anisotropic effects of functional groups in the H-1 NMR have proven to quantitatively be the molecular response property of theoretical spatial nucleus independent chemical shieldings (NICS). Differences between Delta delta(calcd) and Delta delta(exp) were, for the first time, also quantified as arising from steric compression.
N-Substituted 4,4-dimethyl-4-silathiane 1-sulfimides Me2Si(sic)S=NSO2R [R- Ph (1), CF3 (2)] were studied experimentally by variable temperature dynamic NMR spectroscopy. Low temperature 13 C NMR spectra of the two compounds revealed the frozen ring inversion process and approximately equal content of the axial and equatorial conformers. Calculations of the 4-silathiane derivatives 1, 2 and the model compound [R Me (3)] as well as their carbon analogs, the similarly N-substituted (sic)S=NSO2R thiane 1-sulfimides [R = Ph (4), CF3 (5), Me (6)] at the DFT/B3LYP/6-311G(d, p) level in the gas phase and in chloroform solution using the PCM model at the same level of theory showed a strong dependence of the relative stability of the conformer on the solvent. The electronegative trifluoromethyl group increases the relative stability of the axial conformer.
Adequate energy intake in adolescent athletes is considered important. Total energy expenditure (TEE) can be calculated from resting energy expenditure (REE) and physical activity level (PAL). However, validated PAL recommendations are available for adult athletes only. Purpose was to comprise physical activity data in adolescent athletes and to establish PAL recommendations for this population. In 64 competitive athletes (15.3 +/- 1.5yr, 20.5 +/- 2.0kg/m(2)) and 14 controls (15.1 +/- 1.1yr, 21 +/- 2.1kg/m(2)) TEE was calculated using 7-day activity protocols validated against doubly-labeled water. REE was estimated by Schofield-HW equation, and PAL was calculated as TEE:REE. Observed PAL in adolescent athletes (1.90 +/- 0.35) did not differ compared with controls (1.84 +/- 0.32, p = .582) and was lower than recommended for adult athletes by the WHO. In conclusion, applicability of PAL values recommended for adult athletes to estimate energy requirements in adolescent athletes must be questioned. Instead, a PAL range of 1.75-2.05 is suggested.
The syn and anti isomers of cis,cis-tricyclo[5.3.0.0(2.6)]dec-3-ene derivatives have been synthesized and their (1)H and (13)C NMR spectra unequivocally analyzed. Both their structures and their (1)H and (13)C NMR chemical shifts were calculated by DFT, the latter two calculations employing the GIAO perturbation method. Additionally, calculated NMR shielding values were partitioned into Lewis and non-Lewis contributions from the bonds and lone pairs involved in the molecules by accompanying NBO and NCS analyses. The differences between the syn and anti isomers were evaluated with respect to steric and spatial hyperconjugation interactions.
The proportion of the axial conformer increases in the ax reversible arrow eq equilibrium of cyclohexyl acetates (RCOOC(6)H(11), R reversible arrow Me, Et, iPr, tBu, CH(2)Cl, CHCl(2), CO(3). CH(2)Br, CHBr(2), CBr(3)) with the increasing size of the acyloxy substitution. The nature of this unexpected steric substituent effect, which is opposite to general stereochemical concepts, was studied by means of ab kiln MO method, accompanied by NBO and isodesmic calculations. NBO parameters seem to be good descriptors for quantitative prediction of the experimental Delta G degrees value of the title conformational equilibrium. The origin and propagation of the substituent effect of the polar substitutions (CH(2)Cl, CHCl(2), CCl(3), CH(2)Br, CHBr(2), CBr(3)) differ, however, from those of the pure alkyl (Me, Et, iPr, tBu) substitutions. The Delta G degrees value of the polar derivatives depends on the qC8 charges, on the occupation of the sigma(center dot)(C1-07) orbital and on the hyperconjugative pi(center dot)(c=O) -> sigma(center dot)(C10-X) and sigma(center dot)(C10-X) -> pi(center dot)(c=O) interactions. The substituent sensitivity of these NBC parameters for the two conformers differ to the effect that the ax reversible arrow eq equilibrium is shifted to the left side with increasing electron withdrawing character of the acyloxy group. The Delta G degrees values of the alkyl derivatives are interpreted in terms of the calculated dipole moments. The destabilization in the non-polar medium (the experimental Delta G degrees values used were measured in CD(2)Cl(2)) due to the enhanced dipolar character is more prominent in the case of the equatorial alkyl conformers. As the consequence, the ax reversible arrow eq equilibrium is shifted to the left despite the increasing size of the R group when going from Me to tBu substitution.
Background: Athletes may differ in their resting metabolic rate (RMR) from the general population. However, to estimate the RMR in athletes, prediction equations that have not been validated in athletes are often used. The purpose of this study was therefore to verify the applicability of commonly used RMR predictions for use in athletes. Methods: The RMR was measured by indirect calorimetry in 17 highly trained rowers and canoeists of the German national teams (BMI 24 +/- 2 kg/m(2), fat-free mass 69 +/- 15 kg). In addition, the RMR was predicted using Cunningham (CUN) and Harris-Benedict (HB) equations. A two-way repeated measures ANOVA was calculated to test for differences between predicted and measured RMR (alpha = 0.05). The root mean square percentage error (RMSPE) was calculated and the Bland-Altman procedure was used to quantify the bias for each prediction. Results: Prediction equations significantly underestimated the RMR in males (p < 0.001). The RMSPE was calculated to be 18.4% (CUN) and 20.9% (HB) in the entire group. The bias was 133 kcal/24 h for CUN and 202 kcal/24 h for HB. Conclusions: Predictions significantly underestimate the RMR in male heavyweight endurance athletes but not in females. In athletes with a high fat-free mass, prediction equations might therefore not be applicable to estimate energy requirements. Instead, measurement of the resting energy expenditure or specific prediction equations might be needed for the individual heavyweight athlete.
The spatial magnetic properties (through space NMR shieldings-TSNMRS) of metal complexes (with ligands such as acetylacetone, 3-hydroxy-pyran(4) one) and "metallobenzenes" have been calculated by the GIAO perturbation method and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various sizes and directions. The TSNMRS values, thus obtained, can be successfully employed to quantify and visualize partial aromaticity of the metallocyclic ring by comparison with the spatial magnetic properties of the corresponding non-complexed ligands in comparable structural and electronic situations, and benzene, respectively. Because anisotropy/ring current effects in H-1 NMR spectra proved to be the molecular response property of TSNMRS, the results obtained concerning partial "chelatoaromaticity" are experimentally ensured.
The inversion of the flexible five-membered ring in tetrahydrodicyclopentadiene (TH-DCPD) derivatives remains fast on the NMR timescale even at 103 K. Since the intramolecular exchange process could not be sufficiently slowed for spectroscopic evaluation, the conformational equilibrium is thus inaccessible by dynamic NMR. Fortunately, the spatial magnetic properties of the aryl and carbonyl groups attached to the DCPD skeleton can be employed in order to evaluate the conformational state of the system. In this context, the anisotropic effects of the functional groups in the H-1 NMR spectra prove to be the molecular response property of spatial nucleus independent chemical shifts (NICS).
Neuromuscular control in functional situations and possible impairments due to Achilles tendinopathy are not well understood.
Thirty controls (CO) and 30 runners with Achilles tendinopathy (AT) were tested on a treadmill at 3.33 m s(-1) (12 km h(-1)). Neuromuscular activity of the lower leg (tibialis anterior, peroneal, and gastrocnemius muscle) was measured by surface electromyography. Mean amplitude values (MAV) for the gait cycle phases preactivation, weight acceptance and push-off were calculated and normalised to the mean activity of the entire gait cycle.
MAVs of the tibialis anterior did not differ between CO and AT in any gait cycle phase. The activation of the peroneal muscle was lower in AT in weight acceptance (p = 0.006), whereas no difference between CO and AT was found in preactivation (p = 0.71) and push-off (p = 0.83). Also, MAVs of the gastrocnemius muscle did not differ between AT and CO in preactivity (p = 0.71) but were reduced in AT during weight acceptance (p = 0.001) and push-off (p = 0.04).
Achilles tendinopathy does not seem to alter pre-programmed neural control but might induce mechanical deficits of the lower extremity during weight bearing (joint stability). This should be addressed in the therapy process of AT.
Linear mixed models (LMMs) provide a still underused methodological perspective on combining experimental and individual-differences research. Here we illustrate this approach with two-rectangle cueing in visual attention (Egly et al., 1994). We replicated previous experimental cue-validity effects relating to a spatial shift of attention within an object (spatial effect), to attention switch between objects (object effect), and to the attraction of attention toward the display centroid (attraction effect), also taking into account the design-inherent imbalance of valid and other trials. We simultaneously estimated variance/covariance components of subject-related random effects for these spatial, object, and attraction effects in addition to their mean reaction times (RTs). The spatial effect showed a strong positive correlation with mean RT and a strong negative correlation with the attraction effect. The analysis of individual differences suggests that slow subjects engage attention more strongly at the cued location than fast subjects. We compare this joint LMM analysis of experimental effects and associated subject-related variances and correlations with two frequently used alternative statistical procedures
Following up on research suggesting an age-related reduction in the rightward extent of the perceptual span during reading (Rayner, Castelhano, & Yang, 2009), we compared old and young adults in an N+2-boundary paradigm in which a nonword preview of word N+2 or word N+2 itself is replaced by the target word once the eyes cross an invisible boundary located after word N. The intermediate word N+1 was always three letters long. Gaze durations on word N+2 were significantly shorter for identical than nonword N+2 preview both for young and for old adults with no significant difference in this preview benefit. Young adults, however, did modulate their gaze duration on word N more strongly than old adults in response to the difficulty of the parafoveal word N+1. Taken together, the results suggest a dissociation of preview benefit and parafoveal-on-foveal effect. Results are discussed in terms of age-related decline in resilience towards distributed processing while simultaneously preserving the ability to integrate parafoveal information into foveal processing. As such, the present results relate to proposals of regulatory compensation strategies older adults use to secure an overall reading speed very similar to that of young adults.
There has been a substantial increase in the percentage for publications with co-authors located in departments from different countries in 12 major journals of psychology. The results are evidence for a remarkable internationalization of psychological research, starting in the mid 1970s and increasing in rate at the beginning of the 1990s. This growth occurs against a constant number of articles with authors from the same country; it is not due to a concomitant increase in the number of co-authors per article. Thus, international collaboration in psychology is obviously on the rise.
We propose a novel strategy for global sensitivity analysis of ordinary differential equations. It is based on an error-controlled solution of the partial differential equation (PDE) that describes the evolution of the probability density function associated with the input uncertainty/variability. The density yields a more accurate estimate of the output uncertainty/variability, where not only some observables (such as mean and variance) but also structural properties (e.g., skewness, heavy tails, bi-modality) can be resolved up to a selected accuracy. For the adaptive solution of the PDE Cauchy problem we use the Rothe method with multiplicative error correction, which was originally developed for the solution of parabolic PDEs. We show that, unlike in parabolic problems, conservation properties necessitate a coupling of temporal and spatial accuracy to avoid accumulation of spatial approximation errors over time. We provide convergence conditions for the numerical scheme and suggest an implementation using approximate approximations for spatial discretization to efficiently resolve the coupling of temporal and spatial accuracy. The performance of the method is studied by means of low-dimensional case studies. The favorable properties of the spatial discretization technique suggest that this may be the starting point for an error-controlled sensitivity analysis in higher dimensions.
During preclinical development of a gestagenic drug, a significant increase of the total plasma concentration was observed after multiple dosing in pregnant rabbits, but not in (non-pregnant) rats or monkeys. We used a PBPK modeling approach in combination with in vitro and in vivo data to address the question to what extent the pharmacologically active free drug concentration is affected by pregnancy induced processes. In human, a significant increase in sex hormone binding globulin (SHBG), and an induction of hepatic CYP3A4 as well as plasma esterases is observed during pregnancy. We find that the observed increase in total plasma trough levels in rabbits can be explained as a combined result of (i) drug accumulation due to multiple dosing, (ii) increase of the binding protein SHBG, and (iii) clearance induction. For human, we predict that free drug concentrations in plasma would not increase during pregnancy above the steady state trough level for non-pregnant women.